Salicyloylamino-anthraquinone pigments

ABSTRACT

ANTHRAQUINONES ARE DESCRIBED WHICH CONTAIN AT LEAST TWO SALICYLOYLAMINO SUBSTITUENTS IN WHIC SUBSTITUTENTS THE BENZENE NUCLEUS IS SUBSTITUTED BY THESE ANTHRAQUINONES ARE YELLOW OT ORANGE COLOURED PIGR1 BEING HYDROGEN, CHLORINE, BROMINE, THE METHYL, HYDROXYL, METHOXY, CYANO OR PHENYL GROUP OR AN ALKYLSULPHONYL GROUP HAVING 1-4 CARBON ATOMS, AND R2 BEING HYDROGEN, CHLORINE, BROMINE OR THE METHYL GROUP; MENTS OF VERY GOOD WEATHER-AND LIGHT-FSTNESS AND GOOD FASTNESS TO MIGRATION AND OVER-LACQUERING IN SYNTHETIC PLASTIC MATERIALS, AS WELL AS GOOD COLOUR STRENGTH.

United States Patent Us. 01. 260-377 7 Claims ABSTRACT OF THE DISCLOSUREAnthraquinones are described which contain at least two salicyloylaminosubstituents in which substituents the benzene nucleus is substituted byR being hydrogen, chlorine, bromine, the methyl, hydroxyl, methoxy,cyano or phenyl group or an alkylsulphonyl group having 1-4 carbonatoms, and

R being hydrogen, chlorine, bromine or the methyl group;

these anthraquinones are yellow to orange coloured pigments of very goodweatherand light-fastness and good fastness to migration andover-lacquering in synthetic plastic materials, as well as good colourstrength.

DESCRIPTION OF THE INVENTION The present invention concerns newanthraquinone pigments, a process for the production thereof and theapplication of the new compounds for the pigmenting of high molecularorganic material. It is known that l salicylic acid amido-anthraquinonesare suitable as pigments. Pigments of this series are thus known whereinthe salicylic acid radical is substituted by chlorine. These pigmentsusually have a very good lacquers containing aluminium powder. Thecompounds concerned are of the formula wherein at least 2 of the symbolsX X X and X represent an acylamino group, of which at least 2 representa salicylic acid amide group of the Formula II R1 (II) 3,701,791Patented Oct. 31, 1972v and wherein of the symbols X -X at most 4represent 7 chlorine or bromine, at most 2 represent the methyl, cyano,methoxy or ethoxy group and the remainder hydrogen.

These pigments are produced according to the invention by condensingdiamjnoanthraquinones of the Formula III X6 XI 2's in (111) wherein atleast 2 of the symbols X in a-position represent an NH -group, of theremaining symbols X X X X X X X and X at most 4 represent chlorine orbromine, atmost 2 the methyl, cyano, methoxy or ethoxy group, of thesymbols X in a-position at most 2 represent an acylamino group and theremaining symbols X and X denote'hydrogen, with a compound introducingthe salicyl group of the Formula IV HO O I R R, (IV) wherein theradicals R and R have the meaning given in claim 1.

Suitable compounds yielding the salicylic acid radical of the FormulaIII are the corresponding salicylic acids or salicylic acid halides. Thecondensation is advantageously performed in an inert, high-boilingorganic solvent such as chlorobenzene, nitrobenzene, o-dichlorobenzenevor trichlorobenzene, in the presence or absence of condensation agents,optionally by heating with acid-binding agents such as pyridine,quinoline or sodium acetate. In individual cases, depending on thecondensation conditions, oneand the same product may have differentcrystalline modifications.

Suitable starting products for the production of pigments according tothe invention are, e.g. the following aminoanthraquinones:

1,4-diaminoanthraquinone 1,5-diaminoanthraquinone 1,4,5,S-tetraaminozinthraquinone 2,3-dichloro-1,4-diaminoanthraquinone4,8-dichloro-1,S-diaminoanthraquinone2,3-dibromo-1,4-diaminoanthraquinone32,6-dibromo-1,5-diaminoanthraquinone 2-bromo-,1,4-diaminoanthraquinone1 2,4,6,8-tetrabromo-1,S-diaminoanthraquinone2,4,5,7-tetrachloro-1,8-diaminoanthraquinoneZ-methyl-l,4-diaminoanthraquinone 2-methyl- 1,5 -diaminoanthraquinoneZ-methyl-1,8-diaminoanthraquinone 2,6-dimethyl-l,5-diaminoanthraquinone2,7-dimethyl-1,8-diaminoanthraquinone 2-methoxy-1,4diaminoanthraquinone1,5-dimethoxy-4,8-diaminoanthraquinone1,8-dimethoxy-4,5-diaminoanthraquinone 2-ethoxy-1,4-diaminoanthraquinone2,3-dicyano-1,4-diaminoanthraquinone The no further substituted 1,4- or1,5-diaminoanthraquinone, as well as the1,4,5,S-tetraaminoanthraquinone, is preferred.

The salicylic acid amide groups in the pigments, according to theinvention, preferably have chlorine, bromine, methyl or methoxysubstituents.

The pigments according to the invention have in general a good textureand can be frequently used in the form of their crude product. Wherenecessary or desired, the crude products can be converted into a finelydispersed form by grinding or kneading. Grinding auxiliary agents arethereby advantageously used, such as inorganic and/ or organic salts, inthe presence or absence of organic solvents. An improvement in theproperties can often be achieved moreover by heating the crude pigmentsin hot organic solvents. After grinding, the auxiliary agents areremoved inthe usual manner; soluble inorganic salts are removed forexample with water and organic auxiliaries volatile in steam by,'e.g.steam distillation. A reprecipitation from sulphuric acid alsofrequently sufiices to obtain a deeply coloured, finely dispersedpigment. By treating a crystallised crude pigment with organic solvents,by dissolving and reprecipitating with sulfuric acid, as well as bygrinding with salt, other crystalline modifications are obtained.

The pigments according to the invention are suitable for the pigmentingof high molecular organic material and they possess the alreadymentioned good fastness properties. They are used in poster andsheet-metal printing, in printing. inks, for the printing industry, inpaints having an oily base such as in linseed-oil paints, or with anaqueous base such as dispersion paints, or in lacquers of varying kindssuch as in nitrolacquers or stoving lacquers, in the latter case those,for example, having an alkyd resin base. They can also be used for thespinningdyeing of viscose or cellulose acetate, for the pigmenting ofplastics as well as fibers, such as polyethylene, polypropylene,polyurethane, polystyrene, polyesters, polyacrylonitrile, polyamide andpolyvinyl chloride, whereby the latter can also contain softeners, alsofor the pigmenting of celluloseesters, curable resins or for thepigmenting of rubber. The pigments can also be used for dyeing of paperpulp or for the coating of webs, e.g. in the processing of laminatedpaper.

Pigments of particularly good colour strength, weatherfastness,light-fastness, fastness to migration in synthetic plastic materials andto overlacquering are those falling under Formula I in which saidacylamino is selected from alkanoylamino of from 1 to 3 carbon atoms anda benzoylamino radical any substituent of which is selected fromfluorine, chlorine, bromine, methyl, methoxy, nitro and phenyl, and moreparticularly those wherein X and X represent a group of the formulawherein R represents chlorine, bromine, methyl, methoxy or phenyl, and

R represents hydrogen, methyl, chlorine or bromine, and

X X X X X and X represent hydrogen. 1

The following examples illustrate the invention without limiting it inany way. All temperatures are given in degrees centigrade.

Example 1 39.74'g. of 2-hydroxy-3,5-dichloro-l-benzoic acid aresuspended in 400 ml. of anhydrous nitrobenzene and, after the additionof 0.5 ml. of dimethylformamide, 24 g. of thionyl chloride are added tothe suspension. The latter is then heated in 30 minutes to and stirredfor a further hour at this temperature. A dry stream of nitrogen is nowfed into the obtained solution during 15 minutes. A suspension of 19.45g. of 1,5-diaminoanthraquinone in 100 ml. of anhydrous nitrobenzene issubsequently poured in, the mixture stirred for a further 30ininutes at100- and then heated for 3 hours to 160165. After cooling to the yellowproduct of the above gi'ven'formula is filtered off, washed withnitrobenzene at 110", then washed with alcohol and dried at 100 invacuo. By this means are obtained 46 g. of a yellow productwhich, aftersalt milling, yields a deeply-coloured yellow pigment having very goodfastness to light, weather, cross-lacquering and migration. 1

Example 2 0 NH-OO o1 c1- oo-m r 0 A solution of 11.86 g. of thionylchloride in 25 ml. of nitrobenzene is added dropwise in 1 hour, whilestirring well, to a suspension (heated to 105-110") of 9.52 g. ofLS-diaminoanthraquinone and 19.1 g.. of 2-hydroxy-3- 'methyl-5-chloro1-benzoic acid in 250 ml. of nitrobenzene. The yellow suspension isfurther stirred for 30. minutes at 105-110 and then heated for 2 /2hours to 150. After cooling to 100, the yellow crystalline product isfiltered off, .washed with nitrobenzene and alcohol and dried in vacuoat 90100.

In this manner are obtained 20.2 g. of adeeply-coloured yellow pigmentof the above given formula having very good fastness to light,cross-lacquering and migration.

Example I 3 9.52 g. of 1.5-diaminoanthraquinone, 14.6 g. of2-hydroxy-4-methyl-1-benzoic acid and 220 ml. of 1,2,4-trichlorobenzeneare heated while stirring to 105-110. Into the obtained suspension arethen added dropwise in 1 hour, 11.86 g. of thionyl chloride, dissolvedin 25 ml. of 1,2,4-trichlorobenzene. Stirring proceeds at 105-110 untilthe evolution of. hydrochloric acid is completed '(ca. 45 minutes),whereupon the mixture isheated for a further 3 hours to 145-150. Aftercooling to 110?,the pigment of the above formula, precipitated in theform of long orange-red needles, is filtered off, washed ,with1,2,4-trichlorobenzene and alcohol and dried in vacuo at 90-100 18 g. ofa reddish-yellow pigment are thus obtained having a very good fastnessto cross-lacquering, migration and light.

If the 14.6 g. of 2-hydroxy-4-methyl-l benzoic acid are replaced byequimolecular amounts of a 2-hydr0xy-1- benzoic acid listed in thefollowing table, using otherwise the same procedure, pigments are thusobtained having similarly good fastness properties.

TABLE 1 I Shade in No. 2-hydroxy-1-benzoie acid paper printing 4 CHReddish-yellow.

HOOC- 5 Yellow.

HOOC- -CHa 6 Beddish-yelloWL HO- QH3 v H000 -CH HO- -CHa u I Do. 4.11.".

i I Do.

HOOC I 13 (l)CH3 'Do; no I HOOC 14---.-5 i Do.

v i I Do.

' swam No. 2=hydroxy-1-benzoic acid paperprinting 1 :6 i OCHQYellowish-orange.

HOOO- 51st 17 .l 0113 Yellow.

HO u p v,

19 )Bi Do.

Y I I, All Reddish-yellow.

Yellow. SO2CH3 I Example 24 7.14g.. of '1,4-diaminoanthraquinone areheated to -110" with 21.3 g. of 2-hydroxy-3,S-dibromo-l-benzoic. acidand 200 ml. of distilled nitrobenzene. To the obtained suspension arethen added in 1 hour, while stirring well, 892g. of thionyl chloridedissolved in 25 ml. of nitrobenz'ene. After stirring for 30 minutes at105-- the orange-coloured suspension is heated for a further 2% hours to-160. The suspension is then cooled to 100 and the precipitatedorange-red product is filtered. off. It is washed with nitrobenzene,then with alcohol and dried in vacuo at -90100. I Using this procedure,19 g. of a'reddish-yellow pig'- ment of the above given formula areobtained, which has ave'ry good 'fastness to light, cross-lacquering andO] OH O O-HIII IIIH-C O 9.52 g. of 1,8-diaminoanthraquinone are heatedwith 16.6 g. of 2-hydroxy-4-chlorobenzene-l carboxylic acid and 200 ml.of nitrobenzene to 90-95". To the orangered suspension is then addedwithin 1% hours, while stirring well, a solution of 11.86 g. of thionylchloride in 25 ml. of nitrobenzene.v The temperature is raised in 1 hourto 145-150 and stirring is continued for a further 3 hours at thistemperature. After cooling to 90, the orange-red product is filteredoff, washed with nitrobenzene and alcohol and dried. The yield is 18 g.

g. of the finely pulverised pigment of the above given formulav aredissolved at 5-10 in 200 g. of 96% sulphuric acid and then stirred for afurther minutes at this temperature. The solution is then poured into1.5 kg. of ice water in minutes. The product is filtered off, washedfree of acid with water and dried at 60 in vacuo. In this manner isobtained a deeply-coloured, transparent reddish-yellow pigment having avery good fastness to light, cross-lacquering and migration. i

5.4 g. of .1,4,5,S-tetraaminoanthraquinone, 15.8 g. of2-hydroxy-4methyl-benzene-l-carboxylic acid and 200 ml. of ,nitrobenzeneare heated, while stirring, to 105- 110". Into the dark-colouredsuspension are then added dropwise in l hour,12.84 g. of thionylchloride, dissolved in 25 ml. of nitrobenzene. The suspension is heatedwithin 1 hour to 175-180 and's'tirringis continued for a further 3 hoursat this temperature'To complete the reaction, the temperature israised'fo'r a further 30 minutes to 200.After cooling to 'the; brownviolet, fine-crystalline product is filtered off,-washed withnitrobenzene, alcohol and acetone and dried-in *v'acuo at The yieldamounts to 12.4 g. 10 g of the brownviolet pigment of the above givenformula are ground in a l-litr vibratory-mill (containing 3.6 kg. ofiron balls each of 1.5 cm. diameter) with 45 g. of anhydrous calciumchloride and 1.5 g. of a petroleum fraction, boiljng between 150 and230, for 1% hours. 'lfheground material is then extracted with dilutehydrochloric acid,

the residue filtered 01f, washed with water and dried in vacuo at 50-60.By this means is obtained a greenishblue pigment having a soft textureand exhibitinga very good fastness to light, cross-lacquering andmigration.

Example 27 mo -OH -CO-1IIH o r;tH oo-cm mo-oo-r m r m-o0 HO CH:

10.6 g. of 1,5-diacetylamino-4,S-diaminoanthraquinone, 11.9 g. of4-methyl-2-hydroxybenzene-l-carboxylic acid and 200 ml. of nitrobenzeneare heated to -110. Into the blue suspension is then introduced in 1hour a solution of 9.3 g. of thionyl chloride in 25 ml. of nitrobenzene.The temperature is then raised within 2%. hours to 195 and stirringcontinues for a further 2 hours at this temperature. After cooling to100, the precipitated violet product is filtered off, washed withnitrobenzene, alcohol and acetone and dried.

12.5 g. of a pigment of the above given formula are thus obtained which,after milling with salt or reprecipitation from sulphuric acid, yieldsblue dyeings having. a very good fastness to light, cross-lacquering andmigration.

If the 10.6 g. of 1,5-diacetylamino-4,8-diaminoanthraquinone arereplaced by 14.3 g. of 1,5-dibenzoyl-amino- 4,8-diaminoanthraquinone, orequivalent amounts of 1,5 di- (2',4'-dichlorobenzoyl-amino) -4,8-diaminoanthraquinone,

1,5 -di- (4' 11uorobenzoyl-amino)-4,8-diaminoanthraquinone,

1,S-di (2'-bromobenzoyl-amino)-4,8-diaminoanthraquinone, I

1,5-di-(4'-methylbenzoyl-amino)-4,8-diaminoanthraquinone,

1,5-di-(4'-methoxy-3-nitrobenzoy1-amino)-4,8-diaminoanthraquinone,

1,5-di- (4-phenylbenzoyl-amino)-4,8-diaminoanthraquinone,

using otherwise the same procedure, then likewise is obtained a bluepigment possessing similarly good fastness properties.

Example 28 2 parts of the pigment, produced according to Example 3, with36 parts-of hydrate of alumina, 60 parts of linseedoil varnish of mediumviscosity and 0.2 part of cobalt 1inoleate are mixed and triturated onthe three-roller mill. An ink for printing purposes is obtained whichyields reddish-yellow printings having a good degree of purity, hightinctorial strength and exhibiting a very good fastness to light.

Example 29 2 parts of the pigment, produced according to Example 2,together with 10 parts of titanium dioxide, 35 parts of a 60% solutionof a modified urea alkyd resin in a mixture of xylene and butanol in thereciprocal proportion of 1:1, 10 parts of oil of turpentine and 5 partsof xylene are ground for 48 hours in a ball mill. If this colouredlacquer is poured on to aluminium sheet and fixed by stoving for onehour at then a pure yellow dyeing is obtained having a very goodfastness to cross-lacquering, light and weather.

9 Example 30 67 parts of polyvinyl chloride, 33 parts of dioctylphthallate, 2 parts of dibutyl tin dilaurate, 0.6 part of the pigmentproduced according to Example 19, and 2 parts of titanium dioxide aremixed together and rolled for 10-15 minutes at 140. Reddish-yellowpolyvinyl chloride films are obtained having very good fastness tomigration and light.

We claim:

1. A pigment of the formula 005) 12, ll r'n wherein at least two of X XX and X represent acylamino, and at least two of said acylaminorepresent a group of the formula wherein R represents chlorine, bromine,methyl, methoxy, or phenyl and R represents hydrogen, chlorine, bromineor methyl, wherein said acylamino other than is selected from the groupconsisting of alkanoyl-amino of from 1 to 3 carbon atoms and abenzoylamino radical any substituent of which is fluorine, bromine,chlorine, methyl, methoxy, nitro or phenyl, ar'id wherein from zero tofour of X thorugh X represent chlorine or bromine, at most two representmethyl, cyano, methoxy or ethoxy, and the remainder represent hydrogen.

2. A pigment as defined in claim 1, wherein each of X and X represents agroup of the formula wherein R represents chlorine, bromine, methyl,methoxy or phenyl, and R represents hydrogen, methyl, chlorine orbromine,

and X X X X X and X represent hydrogen. 3. A pigment as defined in claim2, which is of the formula 10 4. A pigment as defined in claim 2, whichis of the formula C O-NH 5. A pigment as defined in claim 2, which is ofthe formula HO- OH;

f) NH-C O- 6. A pigment as defined in claim 2, which is of the formula(1) IIIH-C O CO-NH O 7. A pigment as defined in claim 2, which is of theformula LORRAINE A. WEINBERGE'R, Primary Examiner E. J. SKELLY,Assistant Examiner US. Cl. X.R.

8-4, 5, 7, 39, 40; 106-22; 260-37 N, 37 NP, 40 R, 40 TN, 41 C, 372

